Anthbaqttrkrone-nitbosamote compound



Patented Sept. 2?, 332? rsNT orr'i HEINRICH TEECHE AND ALLBERT 39B, ()1? ELBERFELD, NEAR COLOGNE, GEBW, 43 SIGHQES TC! GRASSELLI DYESTUFF CGRP'LR-ATION, OF NEW YORK, N. Y., A. COBPOB-Aw T1115? ill? DEL AWARE.

v .ARTHEAQZFRifiEZE NITROSAMINE CQMPOUN'D.

Io Drawing. Application filed October it, 1825, serial Ho. 82,155, and in Germany October 94, 11:24.

We have found new and useful improvements in anthraquinone-nitrosaminc compounds of which the following, is a clear and exact specification.

It is well known that the action of nitrates and even nitroso compound in presence of acids upon anthraquinone or its derivatives leads to oxidation products. According to the German Patent 251,845, Example a furic acid solution upon anthraquinone and V its derivatives.

We have now found that the action of nitrous acid compounds, such as alkali metal nitrites, ethylnitrite, amylnitrite, etc, upon N-substituted aminoanthraquinones can he so directed as to produce N-nitrosamineanthraquinone bodies of the general formulain which R is an organic radicle, preferably an alkyl, aralkyl, or arvl radicls, e. g. methyl: C A;V be y H5; s r -C,H,; tolvl: -G, H.,-CH, etc. The term nitrous aoi compound as used herein is meant to comprise the nitrosation agents mentioned above, i. e., nitrous acidcits salts and esters. The reaction proceeds in the presence or absence of a diluent, in solution of a mineral acid such ss-not too concentrated sulfuric acid or hydrochloric acid, or of an organic acid such as glacial acetic acid at a temperature below about 40 C. Alpha as well as beta alkyl-, aralkyl or aryl-amino-= anthraquinonecompounds are suitable for our new reaction. The anthraquinone nucleus can itself be substituted in any desired manner.

Our new anthra uinone-nitrosamine compounds are general y yellow colored crystalline prpducts, soluble in sulfuric acid with a yellow color. soluble in sulfuric acid contaming phenol, with a green color, showing 1. 1 part l-methylaminoanthraquinone is:

dissolved in 20 parts hot glacial acetic acid. Sodium nitrite is added to the still hot solution until the color of the solution is a light yellow. Water is now added cautiously and the nitrosamine separates practically uantitatively as beautiful li ht yellow co cred needles. It has most pro hly the formula It can be recrystallized from pyridine. It is soluble in sulfuric acid with a yellow, in phenol-sulfuric acid with a green color; the latter solution shows an absorption spectrum consisting of a sha line in the red part of the spectrum. This nitrosamine is easily decomposed at higher temperature by acids,

reducing agents and even when heated to higher temperature in organic solvents; the

nitroso group is split up inthese reactions. 2. 1 part l-methylaminoanthraquinone is dissolved in 15 parts sulfuric acid, and

a slight excess over the theoretical amount of sodium nitrite added. -The reaction is finished as soon as a drop of the solution when poured into water does not produce an more a red coloration. The reaction mass is then drowned in water and the yellow crysta'lline nitroso compound Se Mates. It is identical with the'product o tained in Example 1.

Thesame product is also obtained if the niethylaminoanthraquinone is dissolved in hydrochloric acid and sodium nitritecallowed torcact upon it..

1 art Lanilido-anthraquinonc is dissolved not in 50 parts glacial acetic acid. After cooling to room temperature sodium nitrite. is added, the nitrosation proceeds and v '10 ine ni-trosu compound separates yc-ilow colored leaflets. I quantitative.

in'oso compouncl which has most formula f the solution turns yellow. .sifuar The yield is is soluble in sulfuric acid with a yellow color and with a green color in phenol-sulfuric acid. The later solution slioivs a distinct arbsorpiion line in the red end of the spectrum.

1 part Lhenzylaminosnthmq inone is solved in. 20-30 parts glacial acetic acid, mid sodium nitrite is added until the color the solution becomes yellow. The reaction mass is diluted with Water and the nii'i'oso compound separates substantially l'n'wfffi as yellow crystalline clusters. It has ,orslmhly the formula i l w x) o solulile in sulfuric acid with a yellow color anal in phenolsulfuric acid with a green solor, which shows an absorption spooinn'consisting of a line in the red. and of ins spectrum.

. 1 part 2methylaminoanthraquinone is L 5x06. in -20 parts glacial 'acetic acid; While hot sodium nitrite is adclezluntil tho orange oolor low. The nitroso compound separates on diii: ..on as beautiful light yellow colored needles. It has most probably the formula oiio'fi It. soluble in sulfuric acid as well as in owanio solvents with yellow: to brownishyollow color. Solutions in phenol-sulfuric s ld. are green and show a distinct absorphon lino in the rod and of the spwtrm'n. This lS -nitsroso-i-methylmninoanthzaqizinone i relatively stable in concentrated sulfuric i l'lil and. organic solvenls even at higher h-mprlrat-ure.

3. 1 port 2-ploluidoanthraquinono is dis HaiYm'l in as litllc glacial acetic acid as posfilaand sodium nitrite added until ihe mimof ihe olution him changed to yellow. in dilution with water the nitrosumine J acid 'wiih gl'esn f the solution changes to yel- 'neissss It is soluble in organic so? 11m acid with a yellow,

absorption spectrum oonsis the red and of the spectrum.

7. 1 part- .Zbenzylaminosni a dissolved in glacial acetic intrits added until ills solu'sl low. The nitro-samins srysallizss tion with water. Reorysfializod dine it forms light yellow colors-z having most probably the formails It is soluble in organi h o phui'ic acid n: sulphurio Sfllii distinci abs-mp6..- the. speoimm,

'We olaim2-- L The nmcsss o T quinonenirossmins oral Formula in whioh. B an ole, whioh com isss acid compound, a about 40 C. upon 9i anthruquinons nompooml 03. Lbs muls w .u CMHYQIMNX in which is an silzyl, smllx'y fl'lyl =ndiole.

- 1 2. The process of promising as a; quinononltrosammo compound sf ill: oral formula sompoond; at temperature below about e10" (1., upon an 5% 1 substitutes ammoanihzraqsinona compound ol the general formula;

in which R is an alkyl, aralkyl or aryl radicle.

3. The process of producing an anthraquinonenitrosamine compound of the general formula in which R is an alkyl, aralkyl or aryl radicle, which comprises reacting, at a temperature below about C., in solution of glacial acetic acid, with a nitrous acid compound upon an N-substituted amino-anthraquinone compound of the general formula in which R is an alkyl, aralkyl or aryl radicle.

4. The process of producing an anthraquinonenitrosamine compound of the gem eral formula in which R is an alkyl, aralkyl or aryl radicle, which comprises reacting at a tempera.- ture below about 46 C., in an acid medium with an alkali-metal nitrite upon an N- substituted amino-anthraquinone compound of the general formula in which R is an alkyl, aralkyl or aryl radicle.

5. The process of producing N-nitroso-2- methylaminoanthraquinone having most probably the formula reacting, at a temperature below about 40 C., in solution of glacial acetic acid with a nitrous acid compound upon 2-methylaminoanthraquinone.

8. The process of producin N-nitroso-Q methylamino-anthraquinone w ich comp1 .ses reacting at a temperature below about 40 (1, in solution of glacial acetic acid with an alkali metal nitrite upon 2-methylaminoanthraquinone.

9. As new products anthraquinone-nitrosamine compounds of the general formula in which R stands for an alkyl, aralkyl or aryl radicle, which are yellow colored crystalline bodies, soluble in organic solvents and in sulfuric acid with a yellow color and soluble in phenol-sulfuric acid with a green color, which shows a distinct absorption line in the red end of the spectrum.

10. As new products anthraquinone-2- nitrosamine compounds of the general formula- N0 ,00 N5 7 O U n in which R stands for an alkyl, aralkyl or aryl radicle, which are yellow colored crystalline bodies, soluble in organic solvents and in sulfuric acid with a yellow color and soluble in phenol-sulfuric acid with a green color showing a distinct absorption line in the red end of the spectrum.

11. As a new product N-nitroso-Q-methylamino-anthraquinone having most probably the formula which forms light yellow colored crystalline needles, soluble in organic solvents and in sulfuric acid with a yellow to yellowish brown color, soluble in phenol-sulfuric acid with a green color showing a distinct absorption line in the red end of the spectrum and which is relatively stable to higher temperatures when dissolved in organlc solvents or concentrated sulfuric acid. J

In testimony whereof we ha ie hereunto set our hands.

HEINRICH TESCHE. ALBERT JOB. 

